17933-29-8Relevant articles and documents
Scott,W.B.,Pincock,R.E.
, p. 2040 - 2041 (1973)
Molecule-induced alkane homolysis with dioxiranes
Fokin,Tkachenko,Korshunov,Gunchenko,Schreiner
, p. 11248 - 11252 (2001)
The mechanisms of C-H and C-C bond activations with dimethyldioxirane (DMD) were studied experimentally and computationally at the B3LYP/6-311+G**//B3LYP/6-31G* density functional theory level for the propellanes 3,6-dehydrohomoadamantane (2) and 1,3-dehydroadamantane (3). The σC-C activation of 3 with DMD (ΔG? = 23.9 kcal mol-1 and ΔGr = -5.4 kcal mol-1) is the first example of a molecule-induced homolytic C-C bond cleavage. The C-H bond hydroxylation observed for 2 is highly exergonic (ΔGr = -74.4 kcal mol-1) and follows a concerted pathway (ΔGr = 34.8 kcal mol-1), in contrast to its endergonic molecule-induced homolysis (ΔG? = 28.8 kcal mol-1 and ΔGr = +9.2 kcal mol-1). The reactivities of 2 and 3 with CRO2Cl2, which follow a molecule-induced homolytic activation mechanism, parallel the DMD results only for highly reactive 3, but differ considerably for more stable propellanes such as 4-phenyl-3,6-dehydrohomoadamantane (1) and 2.
Oxa-adamantyl cannabinoids
Ho, Thanh C.,Tius, Marcus A.,Nikas, Spyros P.,Tran, Ngan K.,Tong, Fei,Zhou, Han,Zvonok, Nikolai,Makriyannis, Alexandros
supporting information, (2021/03/14)
As a continuation of earlier work on classical cannabinoids bearing bulky side chains we report here the design, synthesis, and biological evaluation of 3′-functionalized oxa-adamantyl cannabinoids as a novel class of cannabinergic ligands. Key synthetic steps involve nucleophilic addition/transannular cyclization of aryllithium to epoxyketone in the presence of cerium chloride and stereoselective construction of the tricyclic cannabinoid nucleus. The synthesis of the oxa-adamantyl cannabinoids is convenient, and amenable to scale up allowing the preparation of these analogs in sufficient quantities for detailed in vitro evaluation. The novel oxa-adamantyl cannabinoids reported here were found to be high affinity ligands for the CB1 and CB2 cannabinoid receptors. In the cyclase assay these compounds were found to behave as potent and efficacious CB1 receptor agonists. Isothiocyanate analog AM10504 is capable of irreversibly labeling both the CB1 and CB2 receptors.
2-Azaadamantane N-oxyl (AZADO) and 1-Me-AZADO: Highly efficient organocatalysts for oxidation of alcohols
Shibuya, Masatoshi,Tomizawa, Masaki,Suzuki, Iwao,Iwabuchi, Yoshiharu
, p. 8412 - 8413 (2007/10/03)
Development of a stable nitroxyl radical class of catalysts, 2-azaadamantane N-oxyl (AZADO) and 1-Me-AZADO, for highly efficient oxidation of alcohols is described. AZADO and 1-Me-AZADO exhibit superior catalytic proficiency to TEMPO, converting various sterically hindered alcohols to the corresponding carbonyl compounds in excellent yields. Copyright
Regioselectivity on electroreductive transannular reaction of 7-methylenebicyclo[3.3.1]nonan-3-one
Itoh,Kato,Unoura,Senda
, p. 339 - 345 (2007/10/03)
A competitive transannular reaction occurred to give 7-methyltricyclo[3.3.1.03.7]nonan-3-ol (5) and 1-adamantanol (6) in the non-mediated electroreduction of 7-methylenebicyclo[3.3.1]nonan-3-one (1) in N,N-dimethylformamide. The apparent temperature dependence of the regioselectivity of the reaction may be attributed to the competitive operation of both kinetic and thermodynamic controls in the cyclization of the ketyl radical anion. The differences in the parameter of activation between the 5-exo- and 6-endocyclizations of 1,? ,ΔΔH?(5-exo - 6-endo) and ΔΔS?(5-exo - 6-endo), were evaluated to be -3.1 kcal mol-1 and -11 cal mol-1 K-1, respectively. Semiempirical PM3 (RHF and UHF) calculations were also carried out to elucidate the reaction mechanism.
